Halogenoacetoxyadamantane derivatives and process for production thereof

ABSTRACT

Provided are a novel halogenoacetoxyadamantane derivative which is useful as a modifying agent for a resin for a photoresist and a dry etching resistance-improving agent in the photolithography field, agricultural and medical intermediates and a compound for other various industrial products and a process for producing the same. To be specific, provided are a halogenoacetoxyadamantane derivative having a halogenoacetoxy group in an adamantane skeleton and a process for producing a halogenoacetoxyadamantane derivative, comprising the step of reacting a hydroxyl group of an adamantane skeleton with halogenoacetic halide or reacting the above hydroxyl group with a lithiation agent to derive it into a lithiumoxy group and then reacting halogenoacetic halide to introduce a halogenoacetoxy group.

TECHNICAL FIELD

The present invention relates to a novel halogenoacetoxyadamantanederivative and a process for producing the same. More specifically, thepresent invention relates to a novel halogenoacetoxyadamantanederivative which is useful as a modifying agent for a resin for aphotoresist and a dry etching resistance-improving agent in thephotolithography field, agricultural and medical intermediates and acompound for other various industrial products and a process forefficiently producing the same.

BACKGROUND ART

It is known that adamantane is a compound which has a structure in whichfour cyclohexane rings are condensed in a cage form and which is highlysymmetric and stable and that the derivatives thereof are useful as amedical raw material and a raw material for high functional industrialmaterials since it shows a specific function. For example, it has anoptical characteristic and a heat resistance, so that it is tried to beused for an optical disc substrate, an optical fiber and a lens (referto, for example, Japanese Patent Application Laid-Open No. 305044/1994and Japanese Patent Application Laid-Open No. 302077/1997).

Further, adamantane esters are tried to be used as a resin raw materialfor a photoresist making use of an acid sensitivity, a dry etchingresistance and a UV ray transmittance thereof (refer to, for example,Japanese Patent Application Laid-Open No. 39665/1992).

On the other hand, as a semiconductor element is progressively fined inrecent years, it is required to be further fined at a lithography stepin the production thereof, and therefore investigated are variousmethods for forming fine patterns using photoresist materialscorresponding to irradiated beams having a short wavelength such as KrF,ArF and F₂ eximer laser beams. A novel photoresist material which cancorrespond to irradiated beams having a short wavelength such as theeximer laser beam and the like described above has been desired to bedeveloped.

On the other hand, a halogenoacetoxyadamantane derivative which is anester compound of adamantanol and halogenoacetic acid has an adamantaneskeleton in a molecule, and it is considered to be useful as a modifyingagent for a resin for a photoresist and agricultural and medicalintermediates, but it is a compound which has not so far been known.

DISCLOSURE OF THE INVENTION

In light of the situations described above, an object of the presentinvention is to provide a novel adamantane derivative which is useful asa modifying agent for a resin for a photoresist and a dry etchingresistance-improving agent in the photolithography field, agriculturaland medical intermediates and a compound for other various industrialproducts.

Intensive researches repeated by the present inventors in order todevelop a novel adamantane derivative which is useful for the usesdescribed above have resulted in finding that ahalogenoacetoxyadamantane derivative in which a halogenoacetoxy group isintroduced into an adamantane skeleton is a novel compound which is notdescribed in documents and can meet the object described above and thatthe above compound can efficiently be produced by a specific process.The present invention has been completed based on such knowledge.

That is, the present invention provides:

-   (1) a halogenoacetoxyadamantane derivative characterized by having a    halogenoacetoxy group in an adamantane skeleton,-   (2) the halogenoacetoxyadamantane derivative as described in the    above item (1), wherein the halogenoacetoxy group is a chloroacetoxy    group or a bromoacetoxy group,-   (3) the halogenoacetoxyadamantane derivative as described in the    above item (1) or (2), wherein it is 2-halogenoacetoxyadamantane,    2-alkyl-2-halogenoacetoxyadamantane, 1-halogenoacetoxyadamantane,    1-halogenoacetoxy-3-hydroxyadamantane,    1,3-bis(halogenoacetoxy)adamantane or    1-halogenoacetoxyperfluoroadamantane,-   (4) the halogenoacetoxyadamantane derivative as described in the    above item (3), wherein it is 2-alkyl-2-halogenoacetoxyadamantane,-   (5) the halogenoacetoxyadamantane derivative as described in the    above item (3), wherein it is 1-halogenoacetoxy-3-hydroxyadamantane    and-   (6) a process for producing a halogenoacetoxyadamantane derivative,    comprising the step of reacting a hydroxyl group of an adamantane    skeleton with halogenoacetic halide or reacting the above hydroxyl    group with a lithiation agent to derive it into a lithiumoxy group    and then reacting halogenoacetic halide therewith to introduce a    halogenoacetoxy group.

BEST MODE FOR CARRYING OUT THE INVENTION

The halogenoacetoxyadamantane derivative of the present invention is anovel compound which has a halogenoacetoxy group in an adamantaneskeleton and which is not described in documents, and it can include,for example, compounds represented by Formulas (I-a), (I-b) and (I-c):

wherein R¹ represents a hydrogen atom or an alkyl group having 1 to 10carbon atoms; R² represents a hydrogen atom, a hydroxyl group or aCH₂COO- group; and X represents a halogen atom.

In Formula (I-a) described above, the alkyl group having 1 to 10 carbonatoms out of those represented by R¹ may be either linear or branched,and a lower alkyl group having 1 to 5 carbon atoms is particularlypreferred. The examples of the above alkyl group includes methyl, ethyl,n-propyl, isopropyl, various butyls and various pentyls.

In Formulas (I-a), (I-b) and (I-c), the halogen atom represented by Xincludes fluorine, chlorine, bromine and iodine, and among them,chlorine and bromine are preferred.

The halogenoacetoxyadamantane derivative represented by Formula (I-a)described above is 2-halogenoacetoxyadamantane or2-alkyl-2-halogenoacetoxyadamantane; the halogenoacetoxyadamantanederivative represented by Formula (I-b) is 1-halogenoacetoxyadamantane,1-halogenoacetoxy-3-hydroxyadamantane or1,3-bis(halogenoacetoxy)adamantane; and the halogenoacetoxyadamantanederivative represented by Formula (I-c) is1-halogenoacetoxyperfluoroadamantane. In the present invention, amongthe above halogenoacetoxyadamantane derivatives,2-alkyl-2-halogenoacetoxyadamantane and1-halogenoacetoxy-3-hydroxyadamantane can preferably be given. Thespecific examples of the above 2-alkyl-2-halogenoacetoxyadamantaneinclude 2-chloroacetoxy-2-methyladamantane,2-bromoacetoxy-2-methyladamantane and 2-chloroacetoxy-2-ethyladamantane.Further, the specific examples of 1-halogenoacetoxy-3-hydroxyadamantaneincludes 1-bromoacetoxy-3-hydroxyadamantane.

The halogenoacetoxyadamantane derivatives described above canefficiently be produced by the process of the present invention shownbelow.

In the production process for the halogenoacetoxyadamantane derivativeof the present invention, available are two embodiments, that is, (1) aprocess in which a hydroxyl group in an adamantane skeleton is reactedwith halogenoacetic halide and (2) a process in which the hydroxyl groupin the adamantane skeleton is reacted with a lithiation agent to deriveit into a lithiumoxy group and in which halogenoacetic halide is thenreacted therewith.

In the process (1) described above, adamantanols (II) and halogenoacetichalide (III) are subjected to esterification reaction according to areaction equation (A):

(wherein Ad is an adamantane ring which has or does not have asubstituent; X¹ represents a halogen atom; and X is the same asdescribed above), whereby the targeted halogenoacetoxyadamantanederivative (I) is obtained. When the adamantanols (II) have pluralhydroxyl groups in a molecule, the halogenoacetic halide (III) can bereacted with a part or the whole of the hydroxyl groups.

In the above reaction, the adamantanols (II) used as one of the rawmaterials can include, for example, 2-adamantanol and2-alkyl-2-adamantanol as a raw material for the compound represented byFormula (I-a) described above, 1-adamantanol and 1,3-adamantanediol as araw material for the compound represented by Formula (I-b) andperfluoro-l-adamantanol as a raw material for the compound representedby Formula (I-c).

The halogenoacetic halide (III) which is used as another raw materialincludes, for example, monochloroacetic chloride, monochloroaceticfluoride, monochloroacetic bromide, monobromoacetic chloride,monobromoacetic fluoride and monobromoacetic bromide.

The above reaction can be carried out using a basic catalyst in thepresence or absence of a solvent. The above basic catalyst ispreferably, for example, an organic base such as trimethylamine,triethylamine, pyridine, N,N-dimethylaminopyridine andN,N-dimethylaniline, and they may be used alone or in combination of twoor more kinds thereof. When the solvent is used, the above solventincludes, for example, halogenated hydrocarbon base solvents such asdichloromethane, chloroform, carbon tetrachloride and1,2-dichloroethane, ether base solvents such as diethyl ether,tetrahydrofuran and dioxane, aliphatic hydrocarbon base solvents suchhexane, heptane and octane and aromatic hydrocarbon base solvents suchbenzene, toluene and xylene. The above solvents may be used alone or ina mixture of two or more kinds thereof.

The reaction temperature is selected in a range of usually −78 to 100°C., preferably −78 to 80° C. The reaction pressure is selected in arange of usually 0.1 to 10 MPa. The reaction time is influenced by theconditions such as the reaction temperature and the like and can notdefinitely be determined, and it is usually one hour to 10 days,preferably one hour to 3 days. The concentration of the raw materials inusing the solvent may be optional and shall not specifically berestricted as long as it is not higher than a saturation solubility, andit is preferably 0.5 to 1.0 mole/liter.

On the other hand, in the process (2) described above, a lithiationagent is reacted with the adamantanols (II) according to a reactionequation (B):

(wherein Ad, X and X¹ are the same as described above) to derive theminto lithium adamantyl oxides (IV), and then the halogenoacetic halide(III) is reacted therewith, whereby the targetedhalogenoacetoxyadamantane derivative (I) is obtained. When theadamantanols (II) have plural hydroxyl groups in a molecule, thelithiation agent can be reacted with a part or the whole of the hydroxylgroups, and then the halogenoacetic halide (III) can be reactedtherewith.

In the above reaction, the adamantanols (II) used as one of the rawmaterials include the same ones as explained in the process (1)described above. The lithium adamantyl oxides (IV) corresponding to theminclude lithium 2-adamantyl oxide, lithium 2-alkyl-2-adamantyl oxide,lithium 1-adamantyl oxide, dilithium 1,3-adamantyl dioxide and lithiumperfluoroadamantyl oxide. Also, the lithiation agent includes, forexample, lithium metal, n-butyllithium, sec-butyllithium andtert-butyllithium.

The halogenoacetic halide (III) used as another raw material includesthe same ones as explained in the process (1) described above.

The lithium adamantyl oxides (IV) are reacted with the halogenoacetichalide (III) in the presence of a solvent. The above solvent includes,for example, ether base solvents such as diethyl ether, tetrahydrofuranand dioxane, aliphatic hydrocarbon base solvents such hexane, heptaneand octane and aromatic hydrocarbon base solvents such benzene, tolueneand xylene. The above solvents may be used alone or in a mixture of twoor more kinds thereof.

The reaction temperature is selected in a range of usually −78 to 100°C., preferably −78 to a room temperature. The reaction pressure isselected in a range of usually 0.1 to 10 MPa (G). The reaction time isinfluenced by the conditions such as the reaction temperature and thelike and can not definitely be determined, and it is usually one hour to10 days, preferably one hour to 3 days. The concentration of the rawmaterials may be optional and shall not specifically be restricted aslong as it is not higher than a saturation solubility, and it ispreferably 0.5 to 1.0 mole/liter.

The halogenoacetoxyadamantane derivative of the present invention canefficiently be produced in the manners described above.

The compounds thus obtained can be identified by means of gaschromatography (GC), liquid chromatography (LC), gas chromatography andmass spectroscopy (GC-MS), nuclear magnetic resonance spectroscopy(NMR), infrared spectroscopy (IR) and a melting point-measuring device.

EXAMPLES

Next, the present invention shall be explained in further details withreference to examples, but the present invention shall by no means berestricted by these examples. All operations of feeding throughafter-treatment and storage were carried out under nitrogen flow toprevent penetration of moisture.

Example 1 Production of 2-chloroacetoxy-2-methyladamantane

A 100 ml vessel equipped with a three-way cock was charged with 4.67 g(28.1 millimole) of 2-methyl-2-adamantanol and 2.83 ml (35.0 millimole)of pyridine, and 30 ml of dried tetrahydrofuran was further added todissolve them. Then, a tetrahydrofuran solution containing 4.42 g (39.2millimole) of chloroacetic chloride was dropwise added to the abovesolution by means of a cannula in about 15 minutes under cooling withice. Further, chloroacetic chloride remaining in the vessel was washedwith 10 ml of tetrahydrofuran and joined to the solution. Reaction wascarried out at a room temperature for about 24 hours, and then 300 ml ofwater was added to the reaction liquid to terminate the reaction.

Next, the reaction mixture thus obtained was washed three times withwater and then extracted three times with 100 ml of diethyl ether, andthe extract was dried on anhydrous sodium sulfate. Next, the extract wasconcentrated and then separated and refined by means of a column (silicawas filled therein, and a hexane/diethyl ether mixed solvent (volumeratio 10:1) was used as a developing liquid) to obtain 5.89 g (20.5millimole) of a white solid matter of 2-chloroacetoxy-2-methyladamantane(yield: 72.8 %).

The spectral data are shown below.

Nuclear magnetic resonance spectroscopy (NMR): CDCl₃

1H-NMR (270 MHz): 1.57-2.31 (m, 12H), 1.65 (s, 3H), 4.02 (s, 2H)

¹³C-NMR (68MHz): 22.37, 26.62, 27.30, 32.97, 34.56, 36.18, 38.06, 41.95,89.82, 165.69

Example 2 Production of 2-bromoacetoxy-2-methyladamantane

A 100 ml vessel equipped with a three-way cock was charged with 2.51 g(15.1 millimole) of 2-methyl-2-adamantanol and 1.62 ml (20.0 millimole)of pyridine, and 30 ml of dried tetrahydrofuran was further added todissolve them. Then, a tetrahydrofuran solution containing 6.01 g (30.2millimole) of bromoacetic bromide was dropwise added to the abovesolution by means of a cannula in about 15 minutes under cooling withice. Further, bromoacetic bromide remaining in the vessel was washedwith 10 ml of tetrahydrofuran and joined to the solution. Reaction wascarried out at a room temperature for about 24 hours, and then 300 ml ofwater was added to the reaction liquid to terminate the reaction.

Next, the reaction mixture thus obtained was washed three times withwater and then extracted three times with 100 ml of diethyl ether, andthe extract was dried on anhydrous sodium sulfate. Next, the extract wasconcentrated and then separated and refined by means of a column (silicawas filled therein, and a hexane/diethyl ether mixed solvent (volumeratio 10:1) was used as a developing liquid) to obtain 0.61 g (2.12millimole) of a pale yellow solid matter of2-bromoacetoxy-2-methyladamantane (yield: 14%).

The spectral data are shown below.

Nuclear magnetic resonance spectroscopy (NMR): CDCl₃

¹H-NMR (270 MHz): 1.55-2.30 (m, 12H), 1.63 (s, 3H), 3.80 (s, 2H)

¹³C-NMR (68 MHz): 21.97, 26.49, 26.99, 32.77, 34.41, 35.99, 37.92,65.03, 89.28, 165.32

Example 3 Production of 2-ethyl-2-adamantyl chloroacetate(2-chloroacetoxy-2-ethyladamantane)

A 50 ml vessel equipped with a three-way cock was charged with 1.00 g(5.55 millimole) of 2-ethyl-2-adamantanol and 7.2 ml (8.90 millimole) ofpyridine, and 30 ml of dried tetrahydrofuran was further added todissolve them. Then, a tetrahydrofuran solution containing 0.96 ml (12.0millimole) of chloroacetic chloride was dropwise added to the abovesolution by means of a cannula in about 15 minutes under cooling withice. Further, chloroacetic chloride remaining in the vessel was washedwith 10 ml of tetrahydrofuran and joined to the solution. Reaction wascarried out at a room temperature for about 24 hours, and then 300 ml ofwater was added to the reaction liquid to terminate the reaction.

Next, the reaction mixture thus obtained was washed three times withwater and then extracted three times with 50 ml of diethyl ether, andthe extract was dried on anhydrous sodium sulfate. Next, the extract wasconcentrated and then separated and refined by means of a column (silicawas filled therein, and a hexane/diethyl ether mixed solvent (volumeratio 10:1) was used as a developing liquid) to obtain 0.316 g (1.23millimole) of a white solid matter of 2-ethyl-2-adamantyl chloroacetate(yield: 22.2%).

The spectral data are shown below.

Nuclear magnetic resonance spectroscopy (NMR): CDCl₃

¹H-NMR (270 MHz): 0.81 (t, J=7.29, 3H), 1.57-2.39 (m, 14H), 2.20 (q,J=7.29, 2H), 4.04 (s, 2H)

¹³C-NMR (68MHz): 6.74, 24.76, 27.02, 32.98, 33.45, 34.02, 38.09, 41.62,91.80, 165.32 (C═O)

Example 4 Production of 3-hydroxy-1-adamantyl bromoacetate(1-bromoacetoxy-3-hydroxyadamantane)

A 200 ml vessel equipped with a three-way cock was charged with 0.673 g(4.00 millimole) of 1,3-adamantanediol and 4.37 ml (5.40 millimole) ofpyridine, and 100 ml of dried dioxane was further added, followed byhating the solution up to 95° C. Then, this solution was cooled down to50° C., and a dioxane solution containing 0.35 ml (4.00 millimole) ofbromoacetic bromide was added thereto by means of a cannula. Reactionwas carried out at a room temperature for about 24 hours, and then 300ml of water was added to the reaction liquid to terminate the reaction.

Next, the reaction mixture thus obtained was washed three times withwater and then extracted three times with 30 ml of diethyl ether, andthe extract was dried on anhydrous sodium sulfate. Next, the extract wasconcentrated and then separated and refined by means of a column (silicawas filled therein, and a hexane/diethyl ether mixed solvent (volumeratio 10:1) was used as a developing liquid) to obtain 0.15 g (0.519millimole) of a white solid matter of 3-hydroxy-1-adamantyl bromoacetate(yield: 13.0%).

The spectral data are shown below.

Nuclear magnetic resonance spectroscopy (NMR): CDCl₃

¹H-NMR (270 MHz): 1.54-2.45 (m, 14H), 3.28 (br, 1H), 3.76 (s, 2H)

¹³C-NMR (68 MHz): 31.12 (CH₂), 34.51, 39.56, 43.69, 48.59, 70.31 (C),82.69 (CH₂), 83.35 (C), 165.71 (C═O)

INDUSTRIAL APPLICABILITY

The halogenoacetoxyadamantane derivative of the present invention is anovel compound and is useful as a modifying agent for a resin for aphotoresist and a dry etching resistance-improving agent in thephotolithography field, agricultural and medical intermediates and acompound for other various industrial products.

1. A halogenoacetoxyadamantane derivative comprising a halogenoacetoxygroup in an adamantane skeleton.
 2. The halogenoacetoxyadamantanederivative as claimed in claim 1, wherein the halogenoacetoxy group is achloroacetoxy group or a bromoacetoxy group.
 3. Thehalogenoacetoxyadamantane derivative as claimed in claim 1, wherein saidhalogenoacetoxvadamantane derivative is 2-halogenoacetoxyadamantane,2-alkyl-2-halogenoacetoxyadamantane, 1-halogenoacetoxyadamantane,1-halogenoacetoxy-3-hydroxyadamantane,1,3-bis(halogenoacetoxy)adamantane or1-halogenoacetoxyperfluoroadamantane.
 4. The halogenoacetoxyadamantanederivative as claimed in claim 3, wherein it saidhalogenoacetoxyadamantane derivative is2-alkyl-2-halogenoacetoxyadamantane.
 5. The halogenoacetoxyadamantanederivative as claimed in claim 3, wherein it saidhalogenoacetoxvadamantane derivative is1-halogenoacetoxy-3-hydroxyadamantane.
 6. A process for producing ahalogenoacetoxyadamantane derivative, comprising reacting a hydroxylgroup of an adamantane skeleton directly with halogenoacetic halide orreacting the hydroxyl group with a lithiation agent to derive saidhydroxyl group into a lithiumoxy group and then reacting halogenoacetichalide therewith to introduce a halogenoacetoxy group.